Characterization of organic contaminants and assessment of remediation performance in subsurface formations

ABSTRACT

Characterization of organic contaminants in subsurface formation is performed by methods for detecting the presence of nonaqueous phase liquid in a subsurface formation, and for determining the composition and for determining the volume of nonaqueous phase liquids. Generally the methods comprise introducing one or more partitioning tracers and one or more non-partitioning tracers at one or more injection points located in the subsurface formation and measuring separation between the one or more partitioning tracers and the one or more non-partitioning tracers from one or more sampling points located in the subsurface formation to determine presence, composition and/or volume of nonaqueous phase liquid in the subsurface formation. In addition, the methods can be used to assess the performance of an attempted remediation.

This is a divisional of co-pending application Ser. No. 08/377,742 filedJan. 23, 1995.

FIELD OF INVENTION

This invention concerns methods of detecting the presence ofcontaminants located in subsurface formations, methods of determiningthe composition and/or volume of the contaminants and methods ofassessing the performance of remediation designed to treat or removecontaminants from subsurface formations.

BACKGROUND OF INVENTION

In the 1980's, it became apparent that many hazardous waste sites hadreceived organic liquids, such as petroleum hydrocarbons, chlorinatedsolvents, creosote solutions and coal tars which had subsequentlymigrated into the subsurface beneath these sites. Once in thesubsurface, these liquids dissolved and caused the contamination ofground-water supplies and then proved resistant to their quantitativeremoval by the remedial approaches available. These liquids are known toenvironmental scientists and engineers as non-aqueous phase liquids, or"NAPLs". NAPLs such as petroleum hydrocarbons, which are lighter thanwater, are identified as "LNAPLs", while those denser than water such aschlorinated solvents are known as "DNAPLs".

NAPLs are generally of sufficiently low aqueous solubility andvolatility that their limited dissolution into ground waters orvolatilization into gases has resulted in predictions of their residencein the subsurface for tens, hundreds or perhaps thousands of years.However, their toxicity is often such that their solubilities are manytimes the permitted maximum contaminant levels allowed by the U.S.Environmental Protection Agency in drinking water. For example, the mostcommon NAPL contaminant found in ground waters beneath hazardous wastesites, the metal degreasing solvent trichloroethene, has an aqueoussolubility of 1385 milligrams/liter but a maximum contaminant level of 5micrograms/liter.

Partly because of their ubiquitous use in industry and commerce, lowmaximum contaminant levels and mobility in the subsurface in dissolvedand gaseous states, NAPLs and NAPL constituents, such as benzene derivedfrom gasoline, have come to occupy a central place in the technical andregulatory processes associated with the characterization andremediation of hazardous waste sites. In addition, NAPLs have become thefocus of this concern because of the extreme difficulty in detectingtheir presence. In the context of this discussion, "detection" means theact of inferring the amount, location and/or composition of the NAPL. Inrecent years, a number of knowledgeable observers have commented on thecost and impracticality of detecting DNAPLs using conventionalsite-characterization techniques. See, for example, Huling and Weaver,DNAPL site evaluation, Project Summary, EPA/600/SR-93/022, U.S.Environmental Protection Agency, R.S. Kerr Environmental ResearchLaboratory, Ada, Okla., 74820 (1993); Cohen and Mercer, Dense nonaqueousphase liquids, Ground Water Issue, EPA/540/4-91-002, U.S. EnvironmentalProtection Agency, R.S. Kerr Environmental Research Laboratory, Ada,Okla., 74820 (1989); MacKay and Cherry, "GroundwaterContamination:Pump-and-treat Remediation," Environmental Science andTechnology, 23(6):630-636 (1993).

However, despite the expenditure of billions of dollars annually by theU.S. Government through the Environmental Protection Agency (forinstance, in the implementation of Superfund), the U.S. Department ofEnergy (implementing the Environmental Restoration Program), the U.S.Department of Defense (implementing the Installation RestorationProgram), as well as private corporations, the U.S. EnvironmentalProtection Agency reported in April, 1993 (Cohen and Mercer, 1993) that"relatively little effort has been expended on developing newsite-characterization tools or methods for DNAPL sites." This situationhas resulted in substantive problems for DNAPL site characterization, inparticular because of the tendency of DNAPLs, due to their density andviscosity, to migrate both vertically and laterally from their point ofentry into the subsurface to considerable depth. Consequently, DNAPLsare "largely undetected and yet are likely to be a significant limitingfactor in site remediation" (Huling and Weaver, 1991).

It follows from the sparing solubility and volatility of NAPLs that,generally, the vast majority of the mass of an organic liquid releasedto the subsurface may remain in the NAPL form. Relatively minusculeconcentrations will be present in the dissolved and vapor states, but itis these less important phases that are generally monitored forcompliance with regulations concerning the performance of the remedialoperations at a site (see, Environmental Protection Agency, "Generalmethods for remedial operations performance evaluations,"EPA/600/R092/002, R.S. Kerr Environmental Research Laboratory, Ada,Okla. 74820 (1992)).

SUMMARY OF THE INVENTION

It is now contemplated that one or more problems exist in the area ofNAPL remediation, namely the inability to directly measure NAPLlocation, volume and composition and thereby quantitatively assess theperformance of remedial technologies. Thus, the absence of reliabletools for detecting NAPLs, particularly DNAPLs, prevents successfulremediation or perhaps even containment at hazardous waste sites becauseeffective methods of remediation or containment or both cannot befocused on the source of contamination when the location, amount andperhaps composition of the source are unknown. Furthermore, withoutdirect quantitative measures of NAPL volume and composition, theperformance of remediation technologies cannot be assessed.

The present invention provides a solution to one or more of the needsand disadvantages discussed above. This invention provides a significantdevelopment in the context of contaminant remediation by providing aprocess to, in the first instance, detect whether a NAPL is present. Inaddition, this invention further supplies a method to assess theperformance of an attempted remediation by measuring the volume of NAPLin the subsurface both before and after the attempted remediation. Stillfurther, this invention provides a process for ascertaining thecomposition of the NAPL located in the subsurface prior to remediation,thereby enabling the design of the remediation which is specificallydirected to removal of the thus identified constituents of the NAPL. Theseveral aspects of this invention will now be described.

This invention, in one respect, is a method for detecting the presenceof nonaqueous phase liquid in a subsurface formation, comprising:

(A) introducing one or more partitioning tracers and one or morenon-partitioning tracers at one or more introduction points located inthe subsurface formation;

(B) measuring separation between the one or more partitioning tracersand the one or more non-partitioning tracers from one or more samplingpoints to determine whether nonaqueous phase liquid is present in thesubsurface formation.

This invention, in a second respect, is a method for detecting thepresence of dense nonaqueous phase liquid located in a subsurfaceformation, comprising:

(A) introducing one or more partitioning tracers and one or morenon-partitioning tracers into one or more introduction points located inthe subsurface formation;

(B) measuring separation between the one or more partitioning tracersand the one or more non-partitioning tracers from one or more samplingpoints to determine whether dense nonaqueous phase liquid is present.

This invention, in a third respect, is a method for determining a threedimensional distribution of nonaqueous phase liquid located in asubsurface formation, comprising:

(A) introducing one or more non-partitioning tracers into one or moreinjection points located in the subsurface formation;

(B) withdrawing the one or more non-partitioning tracers and one or morepartitioning tracer from one or more sampling points located in thesubsurface formation;

wherein the introducing occurs at two or more depths or the withdrawingoccurs at two or more depths or wherein both the withdrawing and theintroducing occur at two or more depths;

(C) measuring separation between the one or more non-partitioningtracers and the one or more partitioning tracers from the one or moresampling points to determine the three dimensional distribution ofnonaqueous phase liquid in the subsurface formation.

This invention, in a fourth respect, is a method for determining acomposition of nonaqueous phase liquid located in a subsurfaceformation, comprising:

(A) introducing one or more non-partitioning tracers and two or morepartitioning tracers into one or more introduction points located in thesubsurface formation;

(B) measuring separation between the one or more non-partitioningtracers and the two or more partitioning tracers from one or moresampling points;

(C) comparing the measured separation with reference separation of theone or more non-partitioning tracers and the two or more partitioningtracers when contacted with known nonaqueous phase liquids to determinethe identity of the nonaqueous phase liquids in the subsurfaceformation.

This invention, in a fifth respect, is a method for determining a volumeof dense nonaqueous phase liquid located in a subsurface formation,comprising:

(A) introducing one or more non-partitioning tracers and one or morepartitioning tracers into one or more introduction points located in thesubsurface formation;

(B) measuring separation between the one or more non-partitioningtracers and the two or more partitioning tracers from one or moresampling points to determine the volume of dense nonaqueous phaseliquids in the subsurface formation.

In a sixth respect, this invention is a method for assessing theperformance of attempted remediation of dense nonaqueous phase liquidlocated in a subsurface formation, comprising:

(A) introducing one or more non-partitioning tracers and one or morepartitioning tracers into one or more injection points located in thesubsurface formation;

(B) measuring separation between the one or more non-partitioningtracers and the two or more partitioning tracers from one or moresampling points to determine the volume of dense nonaqueous phaseliquids in the subsurface formation;

(C) performing an attempted remediation to treat or remove nonaqueousphase liquid in the subsurface formation;

(D) repeating steps (A) and (B) to assess performance of the attemptedremediation.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a chromatogram from Example 1 of the normalizedconcentration of tracers plotted against pore volumes.

FIG. 2 shows a chromatogram from Example 2 of the results of apartitioning tracer experiment following remediation.

FIG. 3 shows breakthrough curves from Example 3 after injection oftracers through a clean column.

FIG. 4 shows response curves for light tracers used in Example 3.

FIG. 5 shows response curves for perfluorocarbon tracers used in Example3.

FIG. 6 shows response curves for tracers used in Example 3.

FIG. 7 shows flow rate dependency (partition coefficients) versus flowrate as described in Example 3.

DETAILED DESCRIPTION OF THE INVENTION

The amount of tracer used in the practice of this invention will varydepending on NAPL volume, pore volume of the subsurface to beinvestigated and detection limits of the detection equipment employed.Generally, however, the tracers are employed in an amount such that thetracer concentration at sampling points will exceed a minimum detectionlevels for the analytical instrument suitable for the conditions ofinterest.

Generally, in the first step of the practice of the invention,partitioning and nonpartitioning tracers are introduced into asubsurface formation. The partitioning tracers are characterized ashaving the property of partitioning into the NAPL to a greater extentthan the nonpartitioning tracer such that the partitioning tracertravels in the subsurface formation at a slower rate than thenonpartitioning tracer. For example, depending on the NAPL in thesubsurface formation, a six-carbon alcohol (e.g., dimethylbutanol) mightpartition into the NAPL more than a three-carbon alcohol (e.g.,isopropanol) such that the lighter alcohol travels through thesubsurface formation more rapidly than the heavier alcohol. This conceptis similar to the elution of disparate substances through achromatography bed to separate the disparate substances. The partitioncoefficient of a given tracer provides an indication of the relativepartitioning to be expected in the practice of this invention.Appropriate tracers can be selected from partitioning information toselect at least one nonpartitioning tracer and one or more partitioningtracers (relative to the partition coefficient of the nonpartitioningtracer).

Generally, it is contemplated that the tracers will be introduced intothe subsurface formation via a carrier fluid. In one embodiment of thisinvention, the carrier fluid is a liquid such as water. In anotherembodiment of this invention, the carrier fluid is gaseous at ambienttemperatures, such as air.

A wide variety of tracers can be used in the practice of this inventionand virtually any compound can be used as a tracer with the proviso thatthe tracer has a different composition from the NAPL. Representativeclasses of useful tracers include alcohols, perfluorocarbons,perfluorosulfur compounds, esters, amines, amides, hydrocarbons,sulfates, aldehydes, ketones, as well as salts of bromide and iodide.Representative examples of useful alcohols include C₁ -C₂₀ alcohols andpolyhydric alcohols. Representative examples of useful perfluorocarbonsinclude carbon tetrafluoride (CF₄), octafluorocyclobutane (C₄ F₈),octafluorocyclopentene (C₅ F₈), dodecafluorodimethylcyclobutane (C₆F₁₂), perfluoromethylcyclohexane (C₇ F₁₄) andperfluoro-1,3-dimethylcyclohexane (C₈ F₁₆). When a liquid carrier fluidis employed, preferred tracers are alcohols. When the carrier fluid isgaseous, preferred tracers are perfluorocarbons.

The amounts of tracers will vary widely depending on a variety offactors well known to those skilled in the art. Such factors include butare not limited to the type of tracers employed, the pore volume of thesubsurface formation (pore volume being defined as the volume of porespace encountered by the tracers between the introduction points andsampling points), the NAPL saturation in the subsurface formation(defined as the volume fraction of NAPL per unit pore space in thesubsurface formation), the distance between introduction points andextraction (or "sampling") points, the geology of the subsurfaceformation and the partition coefficients of the tracers.

The tracers used here can be reactive tracers including chemicallyreactive tracers and biologically reactive tracers.

Chemically reactive tracers typically comprise substances such as esterswhich hydrolyze during the practice of this invention to form an alcoholand a carboxylic acid with the resulting alcohol and unreacted esterfunctioning as the tracers. For example, ethyl acetate and propylformate hydrolyze to form, respectively, ethanol and propanol. Use ofchemically reactive tracers is advantageous in circumstances where theintroduction point and the sampling point are at the same location. Theuse of chemically reactive tracers enhances the signal produced in themeasurement equipments. It should be appreciated a soak time may beneeded to enable the tracers to react, such as to hydrolyze. Use ofchemically reactive tracers is not, however, limited to suchapplications. Thus, owing to the relatively short times that tracersspend in the soil traveling along streamlines between wells, reactivetracers could also be used in the practice of any other aspects of thisinvention. Representative examples of useful esters include ethylacetate, methyl acetate, isopropyl acetate, ethyl acetoacetate, ethylacrolate, ethyl methacrolate, ethyl butylate, ethyl benzoate, propylformate, ethyl formate, dimethyl maleate, dimethyl fomarate, dimethylphthalate, dimethyl glutarate, dimethyl succinate, methyl salicylate,methyl methacrylate, methyl acrylate, isobutyl methacrylate, isobutylacrylate, ethylene glycol monomethyl ether acetate, ethylene glycolmonethyl ether acetate, ethylene glycol monobutyl ether acetate, ethyloxalate, ethyl methacrylate, ethyl butylate and ethyl acrylate.

Biologically reactive tracers are substances which respond tomicrobiologically induced reactions indicative of the presence orabsence of NAPL. For instance, such biologically reactive tracers may becapable of being used as a fuel or nutrient for given microorganisms.The use of biologically reactive tracers is envisioned in circumstanceswhere the NAPL present in the subsurface environment is at a level priorto remediation sufficient to suppress the growth of microorganisms. Whenthe given NAPL is removed sufficiently, the microorganisms mayrepopulate the subsurface or increase in population. In such cases, abiologically reactive tracer can be selected which the givenmicroorganism feeds. It can thus be seen that the amount of biologicallyreactive tracer measured would diminish after remediation, therebyindicating a decrease in NAPL in the subsurface formation. For example,sulfates in a sulfate-reducing environment could be induced to reduce tosulfide by action of sulfate-reducing bacteria, the activity formerlybeing suppressed by presence of NAPL prior to remediation.

In another embodiment of the present invention, the tracers can beintroduced into the subsurface formation together with a thickeningagent. Thickening agents are advantageously employed in situations suchas when the NAPL is geologically trapped in the soil, for example, in azone of the permeable soil, whereby the NAPL is more difficult tocontact efficiently with tracers. In such cases, it may be advantageousto include thickening agents with the tracers to provide a more viscousfluid which will slow the water preferentially where no NAPL exists andthereby help force the tracers into the NAPL zone. Food gradewater-soluble polymers are readily available and useful for thispurpose. It is thus apparent that in these applications the thickeningagents serve to exert hydraulic control of the tracers introduced in thesubsurface formation. Additionally, use of thickened tracer fluids maybe advantageous in fractured formations. In such cases, the tendency ofthe water to flow preferentially through the fractures rather than therock matrix that may contain the largest fraction of NAPL. Polymers ofvariable size may be used to advantage. Such large molecules may exhibitsize exclusion effects as in gel permeation chromatography and othersknown to those of skill in the art. Such effects may aid both inplacement of the tracers in the fractured formation and in theinterpolation of the chromatographic signals of the tracers. Usefulthickening agents vary widely but generally include water solublepolymeric substances having a molecular weight in the range from aboutone to about 20 million. Representative classes of useful thickeningagents include polysaccharides, polyglycols and cellulose materials.Representative examples of such thickening agents include xantham gumand carboxy methyl cellulose. The representative classes and examples ofthickening agents is not intended to be an exhaustive list of suchsubstances. The amount of thickening agents used will also varydepending on the amount of thickening desired and will also vary on theinherent viscosity of the thickening agent. Generally, an amount ofthickening agent in the range from about 100 ppm to about 10,000 ppm canbe employed.

The tracers used in the practice of this invention may be introducedinto the subsurface formation by a variety of ways. For instance, thetracers can be introduced simply by digging a hole of desired depth,placing an amount of tracers in the hole and refilling the hole with thematerial previously removed. The tracers can also be introduced into thesubsurface formation by a variety of well known methods employing wellknown means to achieve such methods. For example, tracers can beintroduced by adding the tracers to a well such as an extraction or amonitoring well. Additionally, the tracers can be introduced via apiezometer, a stand pipe, a multilevel sampler, a drive point sampler ora cone-penetration sampling point. The tracers can be added all at once,intermittently or continuously over time. The rate of introduction ofthe tracers is generally not critical and will vary depending on thesize and geology of the subsurface formation. Such rate can bedetermined by one of skill in the art. As discussed above, the amount oftracers employed will also vary depending on the size and geology of thesubsurface formation, but generally will be an amount sufficient suchthat all the tracers introduced are in amounts which can be detected atthe sampling points after the tracers travel a given distance throughthe subsurface formation. It is contemplated that the farther thedistance between introduction point and sampling point, the larger theamount of tracers may be required.

In the practice of this invention, the tracers which have beenintroduced into the subsurface formation can be allowed to travelthrough the subsurface formation thereby allowing the natural gradientsto carry the tracers. Preferably, the tracers are forced into thesubsurface formation as by pumping, i.e. injecting, the tracers. Pumpingmay be accomplished using methods and equipment well known to thoseskilled in the art.

It is contemplated that the tracers can be introduced into thesubsurface formation at one injection point or at multiple injectionpoints. It should be appreciated that when multiple injection points areemployed in the practice of this invention, the injection points maydiffer by depth only or differ from one another by lateral location ordiffer by combinations of different depths and lateral locations. Thus,in one embodiment of the present invention, the tracers can beintroduced into the subsurface formation via a single well at a varietyof depths. In another embodiment of the invention, the tracers can beintroduced into the subsurface formation through multiple wells.

In the practice of this invention, it may be advantageous to minimizeloss of tracer after injection into the subsurface formation byconfinement of the surface. This technique would be particularlyadvantageous when a gaseous carrier fluid is employed. Confinement atthe surface can be achieved as by covering the surface with a sheet ofimpervious material to seal the surface.

The tracers are detected and measured at a sampling point after a timesufficient to enable the tracers to travel through the subsurfaceformation. The sampling point can be at an injection point or can be agiven distance from an injection point. Additionally, a sampling pointcan be in the subsurface formation or, alternatively, the tracers can bewithdrawn above ground and measured thereafter. Preferably, anindividual sampling point is a given distance from a given injectionpoint. The measurement can occur at a sampling point below the surfacesuch as when the measurement equipment is located in the subsurfaceformation or can occur above the subsurface after withdrawing thetracers from the subsurface formation at a sampling point. In principleit may be possible to affect surface detection of the subsurface tracersusing electromagnetic or acoustic signals. Generally, however, detectionis achieved by obtaining a sample of the tracers present (in a carrierfluid if a carrier fluid is used) and measuring any separation oftracers using conventional equipment such as liquid or gaschromatography instruments. It is also contemplated that multiple depthsamplers can be useful in the practice of this invention, as when forexample, a monitoring well is employed at the sampling location.Alternatively, measurement equipment equipped with a ion-selectiveelectrode can be employed when the tracer is an ion such as iodide orbromide.

The chromatography equipment should provide the operator with a readingshowing the separation of tracers. If NAPL is absent from the subsurfaceformation, no separation of tracers should occur, whereas if NAPL ispresent separation should occur. The separation of tracers will enablethe operator to determine the location, volume or composition of NAPL.

From the difference in production times of the tracers, i.e., themeasured separation of tracers at the sampling point, the NAPLsaturation in the subsurface formation can be determined. Using themethod of moments, the volume of total NAPL in the subsurface formationis given by the formula:

    V.sub.N =(V.sub.p -V.sub.n)/K,

where V_(p) and V_(n) are the first moments of the nonpartitioning andpartitioning tracers in terms of cumulative volume of detected tracersat the sampling point, K is the partition coefficient of thepartitioning tracer and V_(N) is the volume of NAPL. This equation orothers similar to it can be applied repeatedly to any number of tracersused in this way. For example, for tracers which are introduced as gases(see, for example, Table 1) the following equation can be employed:

    V.sub.N =q(t.sub.p -t.sub.n)/K.sub.i

wherein K_(i) is the partition coefficient of tracer K_(i) between theNAPL and air, t_(p) and t_(n) are the mean residence times of thepartitioning and nonpartitioning tracers obtained by integrating the twotracer response curves to estimate the first moments of these curves andq is the flow rate [L³ /T]. Additionally, the partition coefficient K ofa gaseous tracer K_(i) is the ratio of its concentration [M/L³ ] in theNAPL phase to its concentration in the gaseous phase, according theformula:

    K.sub.i =C.sub.in /C.sub.ia.

Using thermodynamic phase equilibria theory, partition coefficients forthe various tracers and a particular NAPL may be estimated. Thepartition coefficient of tracer i between NAPL and air was given in anequation above and can be expanded to include mole fractions anddensity, or

    K.sub.i =(C.sub.in /C.sub.ia)=(x.sub.in ρ.sub.N /x.sub.ia ρ.sub.a)=(x.sub.iN V.sub.a)/(x.sub.ia V.sub.N),

where x_(ij) is the mole fraction of tracer i in phase j, V_(a) andV_(N) are the molar volumes of the air and NAPL phases [L³ /mole],respectively, and ρ_(j) is the molar density of that phase. Since thegas phase can be assumed to be ideal at such low pressure, the partitioncoefficient can be estimated from the liquid phase activity coefficientγ_(i) and the vapor pressure of each species i as follows: K_(i)=(PV_(a))/(P_(i) ^(vap) V_(N) γ_(i)), where P is the total pressure[F/L² ], P_(i) ^(vap) is the vapor pressure of the tracer, and γ_(i) isthe activity coefficient for tracer i in the liquid phase. The molarvolume of air at 23° C. is 24,300 cc/mole and the molar volume of TCE is89.99 cc/mole. If the liquid phase were an ideal solution, then theLewis-Randall rule would apply and the activity coefficient of thetracer in the NAPL would be one. These ideal K_(i) values are listed inTable 2 for each tracer with trichloroethene. However, in practice, theliquid can be far from ideal. An activity coefficient model to estimateγ_(i) can be used in such a case. For example, a regular solution theorymodel could be used when the species are not polar. However, such modelsshould be well established for the precise conditions of interest tomake predictions with a high level of confidence.

If the amounts of NAPL in different locations vertically and/or a reallyneed to be determined, the combined chromatographic signal from thetracers needs to be inverted. In many contaminant detection problems,most of the soil will not be contaminated by NAPL, but only a smallamount of NAPL where the source is located. This source often will havecaused a plume of dissolved contaminant to form and migrate over largedistances in ground water, but the source itself will often be small, ofunknown location, and difficult to find by existing technology. A novelaspect of this invention is the use of multi-level tracer injectionpoints and sampling points to solve the inverse problem required todetermine the three-dimensional distribution of NAPL in the soil. Whenthe location of NAPL is desired to be elucidated by the practice of thisinvention, one or more partitioning tracers and one or morenonpartitioning tracers may be introduced at multiple injection pointsor measured at multiple sampling points, or introduced at multipleinjection points and measured at multiple sampling points.

Although most of the NAPL will typically be contained in the source,small amounts will often dissolve in the water and the amount sodissolved may also be of interest. A contaminated unsaturated zonegenerally consists of three fluid phases, namely, residual water,residual NAPL and air. Thus, knowing the residual water saturation maybe valuable as well. In this case, one or more tracers that partitioninto the water from the carrier fluid could be used to estimate theresidual water saturation at the same time that the same or otherpartitioning tracers are used to determine residual NAPL saturation.

The present invention can be employed to determine location, volumeand/or composition of NAPL. It should be appreciated the composition ofthe NAPLs are oftentimes not known and may vary significantly within thesubsurface formation since, in many cases, a wide variety of organicwastes was buried or disposed of over long periods of time in differentpoints of the ground surface without sufficient records. Furthermore,the composition of the NAPL may have changed due to natural processessuch as volatilization into the air, dissolution and so forth. Samplesof air and water containing some of these components are not always areliable indicator of the source composition and liquid samples areoften not available. Tracer partition coefficients are a function of theNAPL composition, so this affects the design and interpretation of thepractice of this invention in the field.

A novel aspect of this invention is the ability through practice of thisinvention to obtain useful results from partitioning tests even insituations where the NAPL composition is only known approximately. Insuch a case, laboratory experiments and/or thermodynamic theory can beused to estimate the K values of each tracer in each major organicspecies (component) of the NAPL. Provided at least as many partitioningtracers are used as there are major organic species (components of theNAPL), then the composition of the NAPL can be inferred as well as theamount of NAPL. This is a second type of inverse problem, known as"compositional analysis," since a solution to the set of equationsdescribing the behavior of the tracers must be estimated from themultiple simultaneous tracer signals.

After the NAPL has been located and one or more of several remediationtechnologies has been applied to remove it from the soil, the quantityremaining in the remediated zone may be estimated to thereby provide aperformance assessment of the attempted remediation. In anotherembodiment of this invention, the quantity of NAPL in the remediationzone can be determined concurrently with the remediation. Thus, themethods of this invention can be employed before, during and afterattempted remediations. To determine volume of NAPL present, onepartitioning tracer and one nonpartitioning tracer need only beintroduced into the subsurface formation.

In one embodiment of the present invention, the distribution of NAPL inthe subsurface formation. In this regard, it is desirable to samplingthe tracers at multiple sampling points and the use of modeling. Inparticular, appropriate injection and sampling points are determined,generally by injecting and/or sampling the tracers at different depths.In some cases, it may be desirable to repeat the tracer testing usingdifferent injection and/or sampling points both with respect to depthand surface location. Once three-dimensional data of this type has beenobtained, a suitable inverse model can be used to calculate athree-dimensional distribution of NAPL. First, a suitable model of thefluid flow behavior of the tracers in the formation is obtained. Thismodel will generally be either a streamline model with suitable featuresto model partitioning tracers or a finite difference or finite elementnumerical model that approximates the differential equations describingthe three-dimensional fluid flow in the formation, but any suitableengineering approach could be used provided it included a description ofthe behavior of the partitioning tracers. Second, an algorithm forcalculating parameters in this model is obtained. This model willgenerally be based upon a maximum likelihood method such as leastsquares regression that can be used to calculate an unknown parametervector so as to fit the fluid flow model predicted values to measureddata in a least squares sense. Such least squares regression algorithmsare known to those of skill in the art, as described in Jin et al.,"Subsurface NAPL Contamination: Partitioning Tracer Test for Detection,Estimation and Remediation Performance Assessment," Toxic Substances andthe Hydrology Sciences, (American Institute of Hydrology, 1994), pages131-159, incorporated herein by reference. The parameters in thisinstance will include the local NAPL saturations or equivalent measuresof NAPL amount locally for discrete volumes of the contaminatedformation under testing. Although other approaches to solving thisinverse problem can be used, including even trial and error, these othermethods will generally be less satisfactory. The forward fluid flowmodel can be used, and is preferably used, to calculate the appropriateinjection and sampling points to design the tracer test for thispurpose.

In addition to estimating the amount and location of NAPL within thecontaminated formation from the partitioning tracer data, it may bedesirable to estimate NAPL composition since many polluted subsurfacewaste sites contain mixtures of various contaminants. If the variouschemical components of this waste mixture are not too dissimilar, asingle organic liquid may be expected to occur within the pores of thecontaminated soil or rock formation, but unless this liquid has beencarefully sampled and analyzed, its precise composition (the set of molefractions of each component in the mixture) will not be known. Estimatesof its composition can sometimes be made from compositional measurementson contaminated water, air or soil that has been sampled and analyzedfrom locations hydraulically connected to the NAPL, but the reliabilityof these will vary depending on the nature of the NAPL and other poorlyknown factors, so additional information about the NAPL composition asinferred from the partitioning tracer test may be desired. This can bedone provided a sufficient number of partitioning tracers are used sincethe partition coefficient of each tracer can be modeled as a function ofNAPL composition and the tracer data inverted to infer composition. Inparticular, each tracer partition coefficient can be expressed as afunction of the activity coefficient of each chemical component in theNAPL or alternatively some other equivalent thermodynamic model can beused to express the relationship between the partition coefficient andcomposition. Activity coefficients depend on the temperature, pressureand n-1 mole fractions, where n is the number of components in the NAPL.The temperature and pressure can be considered known and fixed for anygiven test. This means that n-1 partitioning tracer data sets are neededin principle to infer the n-1 mole fractions describing the unknown NAPLcomposition. In addition, one partitioning tracer data set is needed tocompare with the non-partitioning tracer to infer the NAPL saturation(or equivalently volume or mass) for a total of n partitioning tracersdata sets. Many suitable activity coefficient models are well known andavailable for various types of organic liquids and could be used forthis purpose. Laboratory experiments may be needed in some cases to testor calibrate these models under the conditions of interest and forrepresentative components of NAPL. Laboratory experiments will still beneeded in general to measure the infinite dilution activity coefficientsof the tracer components as a function of NAPL composition, but thetracer concentrations will generally be sufficiently low by design thatthe concentrations of the tracers can be neglected with respect to theactivity coefficient model. Very low concentrations of organiccomponents in the NAPL will for similar reasons not be readily inferredby this approach. Thus, if these very small concentrations are known orsuspected from other data sources or methods, and if they are consideredimportant even though small, then tracers that are particularlysensitive to these components must be selected and used and repeatedapplications of the partitioning tracer method may be needed to targetspecific components or if there is evidence of multiple liquid phases(NAPLs) or significant variations of NAPL composition spatially.Generally, however, these complications will not exist or be importantand the use of n-1 partitioning tracers, where n is now the number ofmajor NAPL components, will serve as a sufficient check on the validityof the measured or assumed NAPL composition. This will be particularlyadvantageous when the method is used as a performance assessment toolsince the NAPL composition will in general change as a result of theremediation process itself. For example, co-solvent may selectivelyextract certain components from certain NAPLs, steam may selectivelydistill lighter components from certain NAPLs, and similarly for mostother remediation processes.

When the tracers are withdrawn, i.e. extracted, from the subsurfaceformation, the methods and apparatus described above for the introducingstep can also be employed. Thus, the tracers can be withdrawn by pumpingusing an extraction or monitoring well, a piezometer, a stand pipe, amultilevel sampler, a drive point sampler or a cone-penetration samplingpoint.

The present invention can be practiced in a variety of subsurfaceformations. Thus, a variety of geological units can be present duringthe practice of the invention. For example, the formation can be uniformand composed of sediment, sediment and rock of varying grain size, rockswith natural fractures and so forth. The present invention can be usedto elucidate the presence of NAPL in fractured subsurface formations, asdiscussed above. The distribution of the nonaqueous phase liquid withinthe subsurface formation can be irregular. Also, the NAPL can be locatedin a substantially unconfined formation.

As described above, the NAPLs characterized in accordance with thisinvention can be LNAPLs (NAPLs less dense than water) or DNAPLs (moredense then water). It is contemplated that the NAPLs constitutecontaminants in the subsurface formation. Generally, NAPLs are organiccompounds or mixtures of organic compounds. Such contaminants may beneeded to be removed from the formation through remediation techniquessuch as described herein. In a given subsurface formation, mixtures ofDNAPLs and LNAPLs may be present. In one embodiment of the invention,DNAPLs are characterized by detecting the presence of the DNAPL,determining the volume of DNAPL, determining the composition of theDNAPL, determining the distribution of the DNAPL or combinationsthereof. Representative classes of NAPLs include halogenatedhydrocarbons including chlorinated hydrocarbons, hydrocarbons such asalkanes and aromatic compounds, ethers, ketone, aldehydes, petroleum oildistillates such as gasoline and aircraft fuel. Representative examplesof DNAPLs include halogenated hydrocarbons such as chlorinatedhydrocarbons, creosote and coal tar. Representative chlorinatedhydrocarbons include chloromethane, methylene dichloride, chloroform,carbon tetrachloride, ethane substituted with from one to six chlorineatoms, ethene substituted with from one to four chlorine atoms,chlorobenzene, dichlorobenzene and trichlorobenzene. Representativeexamples of LNAPLs include hydrocarbons including alkanes, aromaticcompounds such as benzene, alkyl benzene, biphenyl, alkyl biphenyls,ethers, aldehydes, ketones and crude oil distillates such as gasolineand aircraft fuel.

The present invention can be used to initially detect the presence ofNAPL in the subsurface. Additionally, the invention can be carriedrepeatedly to assess the performance of a remediation by determining theinitial volume present of NAPL and then determining the volume presentafter an attempted remediation. Furthermore, the present invention canbe employed to measure the composition of NAPL and/or the volume of NAPLin the subsurface formation.

As used herein, "remediation" means an attempted removal of organiccontaminants (NAPL) from a subsurface formation, which can be performedusing conventional techniques such as the pump and treat methods, orother techniques well known to those skilled in the art of remediation.Remediation may also be performed by use of a surfactant solution whichis pumped in and extracted from the subsurface to remove the organiccontaminants. As used herein, "NAPL saturation" means the volumefraction of NAPL per unit pore space in the subsurface formation. Porespace can be determined by techniques well known to those skilled in theart.

The following examples are provided as exemplary of the practice of thepresent invention and are not to be construed to limit the scope of theinvention or claims thereto. As used in the context of the examples, theinjection points may be referred to as "injection wells" and samplingpoints may be referred to as "production wells".

EXAMPLE 1

Use of Tracers to Determine Presence and Volume of DNAPL inWater-Saturated Sand

A soil column experiment was performed to illustrate the use ofpartitioning tracers to detect DNAPL in a saturated zone. A Kontespreparative chromatography column made of borosilicate glass (4.8 cm ID)was packed with mesh sizes of 60 to 200 Ottawa sand and saturated withwater at 23° C. The length of this sandpack was 12.24 cm. The porosityand intrinsic permeability to water were measured and found to be 0.329and 5.84 Darcy, respectively. Residual tetrachloroethylene (PCE)saturation was established by injecting PCE at a flow rate of 3.31ml/min for 3.1 pore volumes followed by injecting water at a flow rateof 3.0 ml/min for 3.64 pore volumes at which point the effluentcontained only water. Two alcohol tracers were added to the water and0.52 pore volumes of water containing these tracers were injected at0.316 ml/min followed by several more pore volumes of water until thealcohols could no longer be detected in the effluent. The alcohols wereisopropanol (IPA), which partitions to the PCE in only very smallamounts, and 2,3 dimethyl 2-butanol (DMB), which partitions strongly tothe PCE from water. The injected concentration (C_(o)) of IPA was 867mg/l and the injected concentration of DMB (C_(o)) was 873 mg/l. Thepartition coefficients of each of these alcohols were determined byequilibrating samples containing in the range of 100 to 1,000 mg/l ofboth alcohols with equal volumes of water and PCE and measuring thealcohol concentrations in each phase using a gas chromatograph. Thepartition coefficient for IPA determined by this method was found to be0.04 and the value for DMB was 2.76. Both of these values are expressedin mg/l of alcohol in the PCE-rich phase divided by mg/l of alcohol inthe water-rich phase.

The experimental effluent alcohol concentrations are shown in FIG. 1. Asexpected, the DMB was retarded relative to the IPA due to itspartitioning into the residual PCE. The separation of the two curvesgives an unmistakable signal that the sand is contaminated with PCE. Theresidual PCE saturation was estimated using the method of moments to be0.189. This value agrees with the value measured from a mass balance onthe PCE within the experimental error of each of the measurements. Thetracer curves were then numerically simulated using this value and themeasured partition coefficients and these are the curves shown inFIG. 1. Only the dispersivity was adjusted in these simulations. Thevalue determined this way was 0.33 cm, which is typical of valuesmeasured under these conditions. Inverse modeling was also used toestimate the value of the residual PCE using nonlinear least-squaresregression. Each iteration of the computational procedure implementingthe nonlinear least-squares regression requires simulating the tracerdata twice to evaluate the gradients. The value of the residual PCEsaturation computed this way was 0.209.

This experimental example demonstrates that through the practice of thisinvention, NAPL can be detected in a saturated zone. Similar principlesapply to detecting NAPLs in either a saturated or unsaturated zone.There are of course many important details to consider to successfullyapply this technology to the detection of NAPLs in the subsurfaceenvironment. The analysis of the tracer data becomes much morecomplicated and subject to large errors if the tracer velocity is toohigh for local equilibrium. The velocity in this experiment was 2.51ft/day, which gave a residence time of the tracers on the order of 4hours. It is contemplated that this is sufficient residence time to givea close approximation to local equilibrium under these conditions.

Ideally, adsorption of each tracer on the mineral surfaces of the soilshould be zero or close to zero for simplicity. However, if the traceradsorption is measured and it is not too large relative to theretardation due to partitioning into the NAPL, then the calculations canbe done accurately even with tracer adsorption. Equal pore volumes ofadsorption of the tracers will cancel since only the difference betweenthe response curves affects the estimated residual oil saturation. Inany case, adsorption of these alcohol tracers on typical aquifer sand islikely to be negligible compared to the very large partitioning andsubsequent differential retardation due to the residual oil saturationof this experiment.

It is expected that there are a number of other tracer performancecriteria that may be required for field applications. Some of these areenvironmental acceptability, chemical and biological stability,acceptable cost and availability in sufficient quantities, ease ofdetection in the produced fluids, and insensitivity to the precisecomposition of all components of the NAPL, since this may not be knownwith high precision. The tracers used in these examples may or may notmeet all of these criteria and may or may not be ideal choices for thisor any other ground-water condition.

Although less well established, a number of tracers that partitionbetween gas and organic phases have been identified and used. Examplesare light alkanes such as ethane. In a contaminated vadose zone,hydrocarbons that are not present could conceivably be used for thispurpose, but other tracers such as perfluorocarbons are more likely tobe good choices because of their well known and highly desirableproperties and the fact that they will not be present even in very lowquantities in the contaminated zone. Sulfur hexafluoride is stillanother potential tracer for injected air. Although it does partitioninto the organic phase, its partition coefficient may not be largeenough for a strong signal under many conditions of interest. Clearly,there are many other possible water and gas tracers for this purpose andthere are several advantages to using several tracers rather than theminimum of two tracers.

For PCE, IPA has a partitioning coefficient, K, of 0.04 and DMB has apartitioning coefficient, K, of 2.76. The presence of a NAPL, in thiscase PCE, in the sand is inferred by separation of tracers. In FIG. 2 itshould be noted that tritiated water does not partition as does not theIPA to any appreciable degree.

EXAMPLE 2

Performance Assessment of a Remediation

The contaminated sand from Example 1 was cleaned by flushing the sandwith an aqueous solution of surfactant until all the trichloroethene wasremoved to thereby simulate a successful remediation. The procedure ofExample 1 was then repeated. The results are shown in FIG. 2. Since noNAPL is present in which DMB can partition into, the IPA and DMB travelthrough the sand at the same rate and, accordingly, FIG. 2 shows overlapof breakthrough curves of the IPA and DMB. Thus, the absence of NAPL inthe sand can be inferred, thereby indicating a successful remediation.

EXAMPLE 3

Use of Tracers to Determine Presence and Volume of DNAPL in UnsaturatedSand

The perfluorocarbon tracers (PFTs) used in this Example were purchasedfrom PCR, Inc. Table 1 lists some of the properties of the selected PFTsas well as those of the other two gases of interest.

The NAPL used to examine the partitioning of perfluorocarbon gases wastrichloroethylene (TCE, Certified ACS) obtained from Fisher Scientific.The density of TCE at 20° C. is 1.462 g/cc. Its molecular weight is131.39 g/mole and its vapor pressure is 1.16 psi at 20° C.

Ottawa sand, purchased from U.S. Silicon, was used in this experiment.The sand has a size range from 40 to 140 U.S. sieve numbers or 0.425 to0.105 mm. The sand was washed with hydrochloric acid (4N) and baked for24 hours to remove fine materials and possible organics.

Column Procedures

Three columns were prepared for each experiment: (1) a contaminatedprimary column (2.5 cm×30 cm) saturated with residual water and TCE; (2)a contaminated pre-column (2.5 cm×60 cm) saturated with water and TCE;and (3) an uncontaminated secondary column (2.5 cm×30 cm) saturated onlywith water. The contaminated primary column was assembled and weighedwithout sand in order to obtain a reference weight of the column. Thisweight was used later to estimate porosity. Next, the inlet end pieceswere removed and the column was secured to a vibrating jig. Ottawa sandwas placed in a funnel and the funnel was also affixed to the jig. Theapparatus was activated and the column was allowed to fill at a rate ofapproximately 1 cm (of height in column) per minute.

After the primary column was full, it was removed from the stand and theinlet cap tightened onto the end of the column. In addition to the endpieces, three screens (60-150-60 mesh or 0.25-0.0998-0.25 mm) wereplaced on each end in a sandwich fashion. These assist in distributingthe fluid flow and act to keep pressure on the sand pack. Subsequently,the column was leak-tested at a pressure of 10 psi. Finally, the columnwas weighed again and the porosity and pore volume were estimated to be35% and 56.9 cc, respectively. The mean grain density of the sand was2.65 gm/cc.

The contaminated pre-column (2.5 cm×60 cm) was prepared similar to thefirst column. This column saturates incoming air to reduce stripping ofwater and TCE from the primary column that was used to evaluate thetracers.

The primary column was mounted in a vertical configuration and a burettewith 100 cc of deionized water was mounted above the column and attachedto the inlet. The valve on the burette was opened and water was allowedto gravity drain into the column. After approximately one pore volume ofwater had entered the column, the burette was disconnected and thecolumn was allowed to continue to gravity drain. Air was flushed throughthe column to displace any mobile water. The difference between thewater injected and the water produced was used to determine the residualwater saturation. The column was weighed again to verify the waterretained. The residual water saturation was estimated to be 35.9%.

Next, approximately 5 cc of TCE, enough to produce a residualsaturation, was injected into the primary column using a syringe andallowed to gravity drain. After draining overnight, the column wasweighed for a more accurate estimate of TCE saturation. The residual TCEsaturation was estimated to be 8.4%. In both cases, water and TCEinjection, the pre-column was treated in the same manner. However,larger amounts of water and TCE were injected since the pre-column istwice as large.

The primary column and pre-column were plumbed into the flowpath. Airflow was through the precolumn, past the reference side of the thermalconductivity detector (TCD), to the test column and then to themeasurement side of the TCD. Two injectors, one for the gas tracers(Valco Instruments' switching valve with sample loop) and one for liquidtracers (heated injection port) were located between the reference sideof the TCD and the test column. Flow rates were adjusted by the use of asnubber valve located between the precolumn and TCD. Flow rates weremonitored and measured by a combination of rotameters and a bubblemeter. The TCD measures the difference between the reference stream andthe effluent of the test column. Additionally, water-filled manometerswere affixed to each end of the column to measure pressure drops acrossthe column. These measurements were used to estimate the permeability ofthe sand-pack.

Approximately 4 to 8 hours was required for the air stream toequilibrate and for a stable baseline to be established. When thebaseline was stable, tracer injections began. Data collected from theTCD were integrated and the integration values stored to computer filesdata acquisition software.

A secondary, uncontaminated column was packed and configured in the samemanner as the contaminated column. The only modification made to thiscolumn was that the volume of water was equal to the volume of waterplus TCE in the primary column. This secondary column was used toobserve tracer behavior in an uncontaminated environment.

Using the setup described above, several experiments were conducted atvarious flow rates to determine flow rate dependency. Additionally,another test column was prepared containing soil from a field site andthe tracers were evaluated in this medium.

Results and Discussion

Before tracer injection began in the primary column, argon and C₆ F₁₂were injected into the secondary column. Their breakthrough curves areplotted in FIG. 3. Using this procedure, the gas saturation in thesecondary column would be similar to that in the primary column. Thesecondary column was first allowed to equilibrate. Once a baseline wasestablished, argon and C₆ F₁₂ were injected into the column. The C₆ F₁₂was injected as a liquid through the heated injection port. The injectortemperature was 40° C.; the liquid was vaporized and moved through thecolumn as a gas. The purpose of this was twofold, first, to monitor theC₆ F₁₂ with respect to argon; the mean residence times should be similarin a clean column; and second, to observe the breakthrough curve of aliquid tracer (at room temperature and atmospheric pressure) and toexamine it for characteristics that may be particular to tracersinjected as liquids. Several of the tracers in Table 1 are injected asliquids, in particular C₅ F₈, C₆ F₁₂, C₇ F₁₄, C₈ F₁₆. When mixed withair, however, they become gases.

The mean residence times were calculated by the method of moments to be45 cc for both the argon and C₆ F₁₂ tracers in the secondary column. Themean residence times should be equal since there is no TCE for thetracer to partition into. From this result, it can be inferred thatunder these conditions adsorption is negligible. Additionally, the C₆F₁₂, although injected as a liquid, does not exhibit any substantiallydifferent characteristics than argon. The flatness of the peak isbelieved to be a result of the fact that the liquid vaporizes slowly.

After the uncontaminated column experiment had been completed, thecontaminated column experiments were begun. Once a steady baseline onthe chart recorder was achieved with the contaminated column connected,the tracers were injected sequentially into the column and theirproduction was monitored. The mean residence time for production of eachtracer was calculated from the response curves using the method ofmoments. This value can be expressed in minutes or converted to volumeunits by multiplying by the flow rate. Once the mean residence timeswere known, the experimental partition coefficient for each tracer wascalculated. The ratio of the ideal partition coefficient to that of theexperimental value gives the activity coefficient of each tracer in TCE.Table 2 and FIGS. 4, 5 and 6 provide tabular and graphical analysis ofthe results.

Table 2 lists the mean residence time (in minutes and cc), experimentalpartition coefficients, and the activity coefficients calculated foreach tracer. Argon has the shortest retention time followed by CF₄ andSF₆. The small retention time for CF₄ indicates that its partitioning isessentially zero since the value falls within the range of measurementerror compared to argon. However SF₆ does show a small butexperimentally significant partitioning into the TCE. The table showsthat partitioning generally increases with an increase in molecularweight of the tracer.

The computed activity coefficients indicate that high nonideality existsbetween the perfluorocarbon tracers and TCE. The smallest activitycoefficient is 20.3 for C₅ F₈, which is still substantial. The highestwas 63.1 for C₈ F₁₆.

The breakthrough curves are divided into FIGS. 4, 5 and 6. FIG. 4 plotsthe lighter (gas) tracers (argon, SF₆, CF₄ and C₄ F₈) which wereobserved at much higher concentrations than the heavier tracers (C₅ F₈,C₆ F₁₂, C₇ F₁₄, C₈ F₁₆). A volume of 3.5 cc of each gas tracer wasinjected into the column.

FIGS. 5 and 6 show the heavier (liquid) tracers. These tracers areliquids at room temperature and atmospheric pressure. A volume of 0.1 ccof each liquid tracer was injected except 0.05 cc of C₅ F₈ was injected.The produced tracer concentrations of the heavier tracers could beincreased by injecting additional amounts. FIG. 5 does not include C₈F₁₆, because of its delayed production from the column. However, it isincluded in FIG. 6. Clearly the heavier tracers exhibit larger meanresidence times relative to argon, the nonpartitioning tracer. Inaddition, the curve for C₈ F₁₆ shows some asymmetry early in the curvedue to impurities in the tracer.

The tracer response curves generally trend to the right indicatingincreased partitioning. As the tracer partitions into the NAPL phase, itis retained in the column longer therefore its peak is retarded. Thegraphical trend is illustrated by the partition coefficient calculationsreported in Table 2.

The most prominent trend evident in these results is that as the tracersincrease in molecular weight, along with a decrease in vapor pressure,the peak height decreases and there is more spreading at the base of thecurve due to increased partitioning. Compared to the uncontaminatedcolumn, where the argon and C₆ F₁₂ had similar mean residence times,with the addition of TCE to the column, these two tracers now differ inthe primary column by a factor of more than two.

Further experiments at different flow rates provided additional dataabout the tracers. Flow rates of 1.38 cc/min and 4.15 cc/min wereestablished and the suite of tracers were injected sequentially into thecolumn at these flow rates. These rates correspond to linear velocitiesof 2×10⁻⁴ m/s and 6.4×10⁻⁴ m/s. The tracers and their respectivepartition coefficients are listed in Table 3. The negative partitioncoefficient of CF₄ at 4.15 cc/min implies that CF₄ was produced beforeargon for that experiment. Considering all of the data, the conclusionis that CF₄ shows negligible partitioning and should be a good choicefor a nonpartitioning tracer.

These data indicate that equilibrium partitioning was not occurring atthe higher flow rates. Since a rate dependence was observed, the ratewas lowered to 0.08 cc/min and the experiment repeated for C₄ F₈. Inaddition, a batch equilibrium measurement of the partition coefficientwas made for this tracer. Both of these measurements gave a partitioncoefficient of about 4.7, which is significantly higher than the valueof 3.7 at the next lowest rate of 0.45 cc/min. FIG. 7 shows these datafor a batch experiment and all flow rates examined. Based on this datait is contemplated the batch and variable flow rate must be very low inthis column experiment for equilibrium partitioning to occur. Theresidence time at 0.45 cc/min is about two hours and several times thismay be required for equilibrium partitioning. As the partitioncoefficient increases, so does the residence time, so the heaviertracers should be less effected by nonequilibrium partitioning. In anycase, once suitable tracers have been identified, as has been done here,either batch experiments or experiments at low rates or in longercolumns (to give long residence times) can be conducted to determine theequilibrium partitioning coefficients needed for field application(assuming the residence time for the field test is long compared to thecolumn test).

Another experiment was conducted involving the injection of tracers intoa column packed with uncontaminated field soil. The porosity of thefield soil was 42.6%. The permeability was estimated to be about 1.3Darcies; about six times lower than the Ottawa sand. In addition, thefield soil contained clays. The soil was contaminated with TCE in thesame manner as the previous experiments. The tracers were then injectedat two different rates. The lighter tracers (CF₄, C₄ F₈, C₆ F₁₂ and SF₆)were injected at 0.4 cc/min, and the heavier ones (C₅ F₈, C₇ F₁₄ and C₈F₁₆) at 1.2 cc/min. These rates correspond to linear velocities of5.8×10⁻⁵ m/s and 1.7×10⁻⁴ m/s, respectively. Argon was injected at bothrates. The partition coefficients for the various tracers in field soilare given in Table 4. The CF₄ again shows negligible partitioning intothe TCE. The other tracers show partitioning similar to the previousexperiments. The partition coefficient of C₄ F₈ is 4.77, almost the sameas the batch equilibrium measurement. This indicates a closer approachto equilibrium in this experiment even at the rate of 0.4 cc/min.

                  TABLE 1                                                         ______________________________________                                        Properties of Gas Tracers Used in Partitioning Tracer                         Test Experiments                                                                             Molecular Vapor      Boiling                                                  weight    Press      Pt.                                       Tracer         (gm/mole) (psi @ ° C.)                                                                      (° C.)                             ______________________________________                                        Argon, Ar      39.95     --         -186.0                                    Sulfur Hexafluoride, SF.sub.6                                                                146.06     334 @ 21  -63.8                                     Carbon Tetrafluoride, CF.sub.4                                                               88.01     --         -128.0                                    Octafluorocyclobutane, C.sub.4 F.sub.8                                                       200.04      40 @ 21  -5.8                                      Octafluorocyclopentene,                                                                      212.05    12.7 @ 25  27.0                                      C.sub.5 F.sub.8                                                               Dodecafluoroditnethylcyclo-                                                                  300.06     7.2 @ 25  45.0                                      butane, C.sub.6 F.sub.12                                                      Perfluoromethyleyclohexane,                                                                  350.07     2.1 @ 25  76.0                                      C.sub.7 F.sub.14                                                              Perfluoro-1,3- 400.07    0.67 @ 25  101.5                                     dimethylcyclohexane, C.sub.8 F.sub.16                                         ______________________________________                                    

                  TABLE 2                                                         ______________________________________                                        Partition coefficients and activity coefficients from                         partitioning tracer experiment at 0.45 cc/min with Ottawa sand                TCE                                                                                  Mean Residence                Activity                                 Tracer Times       Ideal K.sub.i                                                                           Exp. K.sub.i                                                                          Coefficient,                             i      t.sub.i (mins)                                                                        t.sub.i (cc)                                                                          (C.sub.TCE /C.sub.AIR)                                                                (C.sub.TCE /C.sub.AIR)                                                                γ.sub.i                          ______________________________________                                        Argon  93.2    41.9    0.00    0.00    --                                     SF.sub.6                                                                             103.7   46.7    11.87   1.02    11.6                                   CF.sub.4                                                                             95.1    42.8    --      0.22    --                                     C.sub.4 F.sub.8                                                                      131.4   59.1    99.14   3.73    26.6                                   C.sub.5 F.sub.8                                                                      235.0   105.8   312.54  15.4    20.3                                   C.sub.6 F.sub.12                                                                     204.4   92.0    550.81  10.6    52.0                                   C.sub.7 F.sub.14                                                                     362.6   163.2   1934.45 33.2    58.3                                   C.sub.8 F.sub.16                                                                     1055.0  474.8   5857.20 92.8    63.1                                   ______________________________________                                    

                  TABLE 3                                                         ______________________________________                                        Experimental Partition Coefficients (K.sub.i) at Various                      Flow Rates for Ottawa Sand Contaminated with TCE.                                        K.sub.i (C.sub.TCR /C.sub.AIR) at                                                         K.sub.i (C.sub.TCE /C.sub.AIR) at                      Tracer     1.38 cc/min 4.15 cc/min                                            ______________________________________                                        SF.sub.6   0.04        0.37                                                   CF.sub.4   --          -0.21                                                  C.sub.4 F.sub.8                                                                          2.68        2.49                                                   C.sub.5 F.sub.8                                                                          13.8        12.8                                                   C.sub.6 F.sub.12                                                                         7.53        8.70                                                   C.sub.7 F.sub.14                                                                         --          49                                                     C.sub.8 F.sub.16                                                                         104.5       72.9                                                   ______________________________________                                    

                  TABLE 4                                                         ______________________________________                                        Experimental Partition Coefficients (K.sub.i) and Activity                    Coefficients (γ.sub.i) in Field Soil Contaminated with TCE.                                     Activity                                              Tracer       K.sub.i (C.sub.TCE /C.sub.AIR)                                                           Coefficient, γ.sub.i                            ______________________________________                                        SF.sub.6     0.69       17.2                                                  CF.sub.4     0.12       --                                                    C.sub.4 F.sub.8                                                                            4.77       20.8                                                  C.sub.5 F.sub.8                                                                            18.2       17.2                                                  C.sub.6 F.sub.12                                                                           12.3       45                                                    C.sub.7 F.sub.14                                                                           36.8       52.6                                                  C.sub.8 F.sub.16                                                                           65.3       89.7                                                  ______________________________________                                    

It should be appreciated that additional materials can be added alongwith the tracers during the practice of this invention. However, itshould also be appreciated that this invention can be practiced in theabsence of other substances or in the absence of other procedures duringthe practice of this invention. Thus, the present invention may bepracticed in the absence of surfactants which might deleteriously effectthe partitioning of tracers in the NAPL.

What is claimed is:
 1. A method for determining a volume of totalnonaqueous phase liquid located in a subsurface formation,comprising:(A) introducing one or more non-partitioning tracers and oneor more partitioning tracers into one or more injection points locatedin the subsurface formation; (B) measuring separation between the one ormore non-partitioning tracers and the one or more partitioning tracersfrom one or more sampling points to determine the volume of totalnonaqueous phase liquid in the subsurface formation.
 2. The method ofclaim 1, wherein the tracers are introduced at two or more injectionpoints located in the subsurface formation the two or more injectionpoints being at different depths.
 3. The method of claim 1, whereinsamples are taken at two or more sampling points located in thesubsurface formation, the two or more sampling points being at differentdepths.
 4. The method of claim 1, wherein the injection point and thesampling point are the same.
 5. The method of claim 1, wherein thenonaqueous phase liquid comprises one or more components, and furthercomprising determining a composition of the one or more nonaqueous phaseliquids by comparing the measured separation with a reference separationof the one or more non-partitioning tracers and the two or morepartitioning tracers when contacted with reference nonaqueous phaseliquids the composition of the nonaqueous phase liquid by:expressingeach tracer partitioning coefficient as a function of activitycoefficients for two or more of said components; and calculating therespective mole fractions for each of said two or more components andvolume of total nonaqueous phase liquid by simultaneously solving thefollowing equation expressed in terms of each of said components andsaid volume of total nonaqueous phase liquid:

    V.sub.n =(V.sub.p -V.sub.n)/K

where: V_(p) =the first moment of one of said partitioning tracers interms of cumulative volume of detected tracer at the sampling point;V_(n) =the first moment of one of said nonpartitioning tracers in termsof cumulative volume of detected tracer at the sampling point; K is thepartition coefficient of one of said partitioning tracers; and V_(N) isthe volume of total NAPL.
 6. The method of claim 1, wherein thedistribution of the nonaqueous phase liquid is irregular.
 7. The methodof claim 1, wherein the nonaqueous phase liquid is located in asubstantially unconfined formation.
 8. The method of claim 1, whereinone or more of the one or more partitioning tracers are reactivetracers.
 9. The method of claim 8, wherein at least one of the reactivetracers is chemically reactive.
 10. The method of claim 8, wherein atleast one of the reactive tracers is biologically reactive.
 11. Themethod of claim 1, wherein a thickening agent is introduced with thetracers.
 12. The method of claim 1, wherein said nonaqueous phase liquidis a dense non-aqueous phase liquid.
 13. The method of claim 12, whereinthe dense nonaqueous phase liquid is a chlorinated hydrocarbon, creosoteor coal tar.
 14. The method of claim 12, wherein the tracers areintroduced at two or more injection points located in the substrateformation, the two or more injetion points being at different depths.15. The method of claim 12, wherein samples are taken at two or moresampling points located in the subsurface formation, the two or moresampling points being at different depths.
 16. The method of claim 12,wherein the injection point and the sampling point are the same.
 17. Themethod of claim 12, wherein the dense nonaqueous phase liquid comprisesone or more components, and further comprising determining thecomposition of the nonaqueous phase liquid by:expressing each tracerpartitioning coefficient as a function of activity coefficients for twoor more of said components; and calculating the respective molefractions for each of said two or more components and volume of totalnonaqueous phase liquid by simultaneously solving the following equationexpressed in terms of each of said components and said volume of totalnonaqueous phase liquid:

    V.sub.n =(V.sub.p -V.sub.n)/K

where: V_(p) =the first moment of one of said partitioning tracers interms of cumulative volume of detected tracer at the sampling point;V_(n) =the first moment of one of said nonpartitioning tracers in termsof cumulative volume of detected tracer at the sampling point; K is thepartition coefficient of said partitioning tracers; and V_(N) is thevolume of total NAPL.
 18. The method of claim 17, wherein the number ofpartitioning tracers is equal to or greater than the number ofcomponents whose presence is determined.
 19. The method of claim 12,wherein the dense nonaqueous phase liquid is a chlorinated hydrocarbon,creosote or coal tar.
 20. The method of claim 12, wherein thedistribution of the dense nonaqueous phase liquid is irregular.
 21. Themethod of claim 12, wherein the dense nonaqueous phase liquid is locatedin a substantially unconfined formation.
 22. The method of claim 12,wherein one or more of the one or more partitioning tracers are reactivetracers.
 23. The method of claim 22, wherein at least one of thereactive tracers is chemically reactive.
 24. The method of claim 22,wherein at least one of the reactive tracers is biologically reactive.25. The method of claim 12, wherein a thickening agent is introducedwith the tracers.
 26. The method of claim 12, wherein said volume oftotal dense nonaqueous phase liquid in said subsurface formation isdetermined using the following equation:

    V.sub.n =(V.sub.p -V.sub.n)/K

where: V_(p) =the first moment of one of said partitioning tracers interms of cumulative volume of detected tracer at the sampling point;V_(n) =the first moment of one of said nonpartitioning tracers in termsof cumulative volume of detected tracer at the sampling point; K is thepartition coefficient of one of said partitioning tracers; and V_(N) isthe volume of total NAPL.
 27. The method of claim 12, wherein one ormore of the partitioning tracers is a substance which hydrolyzes to forman alcohol and a carboxylic acid.
 28. the method of claim 12, whereinone or more of the partitioning tracers is capable of being used as afuel or nutrient for microorganisms.
 29. The method of claim 1, whereinsaid volume of total nonaqueous phase liquid in said subsurfaceformation is determined using the following equation:

    V.sub.n =(V.sub.p -V.sub.n)/K

where: V_(p) =the first moment of one of said partitioning tracers interms of cumulative volume of detected tracer at the sampling point;V_(n) =the first moment of one of said nonpartitioning tracers in termsof cumulative volume of detected tracer at the sampling point; K is thepartition coefficient of one of said partitioning tracers; and V_(N) isthe volume of total NAPL.
 30. The method of claim 1, wherein one or moreof the partitioning tracers is a substance which hydrolyzes to form analcohol and a carboxylic acid.
 31. The method of claim 1, wherein one ormore of the partitioning tracers is capable of being used as a fuel ornutrient for microorganisms.
 32. The method of claim 1, wherein thepresence or absence of nonaqueous phase liquid in said subsurfaceformation is unknown.
 33. A method for determining a volume of totalnonaqueous phase liquid located in a subsurface formation,comprising:(A) introducing one or more non-partitioning tracers and oneor more partitioning tracers into one or more injection points locatedin the subsurface formation, in which the presence or absence ofnonaqueous phase liquid is unknown; and (B) measuring separation betweenthe one or more non-partitioning tracers and the one or morepartitioning tracers from one or more sampling points to determine thevolume of total nonaqueous phase liquid in the subsurface formation. 34.The method of claim 33, wherein one or more of the one or morepartitioning tracers are reactive tracers.
 35. The method of claim 33,wherein said volume of total nonaqueous phase liquid in said subsurfaceformation is determined using the following equation:

    V.sub.n =(V.sub.p -V.sub.n)/K

where: V_(p) =the first moment of one of said partitioning tracers interms of cumulative volume of detected tracer at the sampling point;V_(n) =the first moment of one of said nonpartitioning tracers in termsof cumulative volume of detected tracer at the sampling point; K is thepartition coefficient of one of said partitioning tracers; and V_(N) isthe volume of total NAPL.
 36. The method of claim 33, wherein saidnonaqueous phase liquid is a dense non-aqueous phase liquid.
 37. Themethod of claim 36, wherein the distribution of the dense nonaqueousphase liquid is irregular.
 38. The method of claim 36, wherein the densenonaqueous phase liquid is located in a substantially unconfinedformation.
 39. The method of claim 36, wherein the dense nonaqueousphase liquid is a chlorinated hydrocarbon, creosote or coal tar.
 40. Themethod of claim 33, wherein the nonaqueous phase liquid comprises one ormore components, and further comprising determining the composition ofthe nonaqueous phase liquid by:expressing each tracer partitioningcoefficient as a function of activity coefficients for two or more ofsaid components; and calculating the respective mole fractions for eachof said two or more components and volume of total nonaqueous phaseliquid by simultaneously solving the following equation expressed interms of each of said components and said volume of total nonaqueousphase liquid:

    V.sub.n =(V.sub.p -V.sub.n)/K

where: V_(p) =the first moment of one of said partitioning tracers interms of cumulative volume of detected tracer at the sampling point;V_(n) =the first moment of one of said nonpartitioning tracers in termsof cumulative volume of detected tracer at the sampling point; K is thepartition coefficient of one of said partitioning tracers; and V_(N) isthe volume of total NAPL.
 41. The method of claim 40, wherein the numberof partitioning tracers is equivalent to one more than the number ofcomponents whose presence is determined.